Methods Of Etching Trenches Into Silicon Of A Semiconductor Substrate, Methods Of Forming Trench Isolation In Silicon Of A Semiconductor Substrate, And Methods Of Forming A Plurality Of Diodes

ABSTRACT

A method of etching trenches into silicon of a semiconductor substrate includes forming a mask over silicon of a semiconductor substrate, with the mask comprising trenches formed there-through. Plasma etching is conducted to form trenches into the silicon of the semiconductor substrate using the mask. In one embodiment, the plasma etching includes forming an etching plasma using precursor gases which include SF 6 , an oxygen-containing compound, and a nitrogen-containing compound. In one embodiment, the plasma etching includes an etching plasma which includes a sulfur-containing component, an oxygen-containing component, and NF x .

TECHNICAL FIELD

Embodiments disclosed herein pertain to methods of etching trenches intosilicon of a semiconductor substrate, to methods of forming trenchisolation in silicon of a semiconductor substrate, and to methods offorming a plurality of diodes.

BACKGROUND

In the fabrication of integrated circuitry, numerous devices are packedinto a small area of a semiconductor substrate to create an integratedcircuit. Many of the individual devices are electrically isolated fromone another. Accordingly, electrical isolation is an integral part ofsemiconductor device design for preventing unwanted electrical couplingbetween adjacent components and devices.

As the size of integrated circuits is reduced, the devices that make upthe circuits are positioned closer together. Conventional methods ofisolating circuit components include trench isolation. Such occurs byetching trenches into a semiconductor substrate and filling the trencheswith insulative material. As the density of components on thesemiconductor substrate has increased, the widths of the trenches havedecreased. Further, the depths of the trenches have tended to increase.One type of semiconductor substrate material within which isolationtrenches are formed is crystalline silicon, and which may include othermaterials such as germanium and/or conductivity modifying dopants. Aneed remains for developing improved etching chemistries which enabletrenches to be etched into silicon, for example in the fabrication oftrench isolation.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagrammatic isometric view of a portion of a semiconductorsubstrate in process in accordance with an embodiment of the invention.

FIG. 2 is a sectional view of the FIG. 1 substrate taken through line2-2 in FIG. 1.

FIG. 3 is a view of the FIG. 2 substrate at a processing subsequent tothat shown by FIG. 2.

FIG. 4 is a view of the FIG. 3 substrate at a processing subsequent tothat shown by FIG. 3.

FIG. 5 is a view of the FIG. 1 substrate at a processing subsequent tothat shown by FIG. 4.

FIG. 6 is a sectional view of the FIG. 5 substrate taken through line5-5 in FIG. 5.

FIG. 7 is a sectional view of the FIG. 5 substrate taken through line7-7 in FIG. 5.

FIG. 8 is a view of the FIG. 5 substrate at a processing subsequent tothat shown by FIG. 5.

FIG. 9 is a sectional view of the FIG. 8 substrate taken through line9-9 in FIG. 8.

FIG. 10 is a sectional view of the FIG. 5 substrate taken through line10-10 in FIG. 8.

FIG. 11 is a view of the FIG. 8 substrate at a processing subsequent tothat shown by FIG. 8.

FIG. 12 is a sectional view of the FIG. 11 substrate taken through line12-12 in FIG. 11.

FIG. 13 is a sectional view of the FIG. 11 substrate taken through line13-13 in FIG. 11.

FIG. 14 is a view of the FIG. 11 substrate at a processing subsequent tothat shown by FIG. 11.

FIG. 15 is a sectional view of the FIG. 14 substrate taken through line15-15 in FIG. 14.

FIG. 16 is a sectional view of the FIG. 14 substrate taken through line16-16 in FIG. 14.

FIG. 17 is a view of the FIG. 14 substrate at a processing subsequent tothat shown by FIG. 14.

FIG. 18 is a sectional view of the FIG. 17 substrate taken through line18-18 in FIG. 17.

FIG. 19 is a sectional view of the FIG. 17 substrate taken through line19-19 in FIG. 17.

FIG. 20 is a view of the FIG. 19 substrate at a processing subsequent tothat shown by FIG. 19.

FIG. 21 is a view of the FIG. 17 substrate at a processing subsequent tothat shown by FIG. 20.

FIG. 22 is a sectional view of the FIG. 21 substrate taken through line22-22 in FIG. 21.

FIG. 23 is a sectional view of the FIG. 21 substrate taken through line23-23 in FIG. 21.

FIG. 24 is a view of the FIG. 21 substrate at a processing subsequent tothat shown by FIG. 21.

FIG. 25 is a sectional view of the FIG. 25 substrate taken through line25-25 in FIG. 24.

FIG. 26 is a sectional view of the FIG. 25 substrate taken through line26-26 in FIG. 24.

DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS

Embodiments of the invention include methods of etching trenches intosilicon of the semiconductor substrate, and also methods of formingtrench isolation in silicon of the semiconductor substrate. Further,embodiments of the invention also include methods of forming a pluralityof diodes.

Referring initially to FIGS. 1 and 2, a semiconductor substrate isindicated generally with reference numeral 10. In the context of thisdocument, the term “semiconductor substrate” or “semiconductivesubstrate” is defined to mean any construction comprising semiconductivematerial, including, but not limited to, bulk semiconductive materialssuch as a semiconductive wafer (either alone or in assemblies comprisingother materials thereon), and semiconductive material layers (eitheralone or in assemblies comprising other materials). The term “substrate”refers to any supporting structure, including, but not limited to, thesemiconductive substrates described above. Substrate 10 is depicted ascomprising a bulk semiconductor substrate, for example comprisingmonocrystalline silicon 12, although other silicon-comprising substratessuch as semiconductor-on-insulator and other substrates might be used.Material 12 may include other materials, for example germanium and/orconductivity modifying dopants. In one embodiment, bulk silicon material12 comprises a p-type bulk region 14 that is doped to any suitable p−level doping. Thereabove are sequentially depicted an n-type doped n+region 16, an n-type n− doped region 18, and a p-type p+ doped region20. Alternate silicon-containing substrates are also of coursecontemplated.

A series of masking layers is received above silicon material 20. Suchincludes a pad oxide layer 22, a silicon nitride or polysilicon layer24, a hardmasking layer 26, an antireflective coating layer 28, and apatterned photoresist layer 30. Any of such layers are optional, and maycomprise multiple different materials and/or layers with respect toeach. Such materials may or may not be ultimately sacrificial. Incertain embodiments, hardmask layer 26 may be any of insulative,semiconductive, or conductive. Example insulative materials for hardmasklayer 26 include silicon dioxide, whether doped or undoped, as well assilicon nitride. Example conductive materials for hardmask layer 26include any one or combination of refractory metal nitrides (i.e., TiN,WN, etc.), refractory metal silicides (WSi_(x), TiS_(x), etc.), or anymetal in elemental form (Ti, W, etc.). Photoresist 30 is depicted ashaving been patterned to form trenches 32 to antireflective coatinglayer 28.

Referring to FIG. 3, photoresist 30 (not shown) and antireflectivecoating layer 28 (not shown) have been used as a mask to etch throughhardmask layer 26, with photoresist layer 30 and antireflective coating28 being removed at least in part by such etching and/or subsequently.An example anisotropic dry etching chemistry for conducting the sameincludes SO₂+O₂ or O₂+HBr, or O₂+N₂ for the photoresist, and for theantireflective coating generally one or more fluorocarbons, for exampleCF₄,+HBr+He.

Referring to FIG. 4, patterned hardmask layer 26 has been used as a maskfor etching through layers 24 and 22, thereby extending trenches 32ultimately to silicon 12. An example etching chemistry for etchingthrough a silicon nitride layer 24 includes one or morefluorocarbon+SF6+NF3, while an example etching chemistry for clearingpad oxide 22 thereafter includes one or more fluorocarbons, for exampleCF₄, CHF₃, CH₂F₂, etc. FIG. 4 thereby depicts, in but one exampleembodiment, the formation of a mask 35 over silicon of the semiconductorsubstrate, with mask 35 comprising trenches 32 formed there-through.Such mask may or may not include a hardmask layer, and in but oneexample can be considered as a first mask comprising first trenches 32formed there-through which run in a first major direction over substrate10. The example first major direction in the depiction of FIG. 4 wouldbe perpendicularly into and out of the plane of the page upon which FIG.4 lies. Of course, first trenches 32 might not be entirely straight insuch direction and might, by way of example only, serpentine relative toeach other but nevertheless, in one embodiment, run in a first majordirection over the substrate as just described.

Referring to FIGS. 5, 6, and 7, trenches 32 have been extended relativeto substrate 10 by plasma etching into silicon 12 thereof using mask 35.In one embodiment, the plasma etching comprises forming an etchingplasma using precursor gases comprising SF₆, an oxygen-containingcompound, and a nitrogen-containing compound. The oxygen-containingcompound and the nitrogen-containing compound might comprise differentcompounds, and/or might comprise the same compound. For example in oneembodiment, the oxygen-containing compound comprises O₂, and thenitrogen-containing compound comprises N₂. An example oxygen-containingcompound and nitrogen-containing compound encompassed by the samecompound includes NO_(x), where “x” ranges from, for example, about 1 to3.

Further of course, the precursor gases might comprise twooxygen-containing compounds, for example with one of theoxygen-containing compounds being void of nitrogen and another of theoxygen-containing compounds comprising nitrogen. For example in but oneembodiment, the precursor gases might comprise SF₆, N₂, O₂, and NO_(x).Alternately in such example, the precursor gases from which the plasmaetching occurs might not include N₂. Further in one embodiment, theprecursor gases might comprise, consist essentially of, or consist ofSF₆, O₂, and N₂. Additional precursor gases might also of course beutilized, for example HBr. In one embodiment, the precursor gases fromwhich the plasma etching is conducted might comprise more N₂ than eachof SF₆ and O₂ where such three gases are used. In one embodiment, themask used during the etch comprises an outermost hardmask layer duringat least a latter portion of the plasma etching into the silicon, and inone embodiment such outer mask layer is void of carbon as the statedplasma etching chemistry may etch an outermost hardmask layer thatcomprises carbon.

The invention was reduced to practice using a LAM Kiyo plasma etchingchamber. Regardless and by way of examples only, example pressure duringetching may be from about 1 mTorr to about 50 mTorr, and an exampletemperature range for the susceptor upon which the substrate rests isfrom about 0° C. to about 50° C. An example source power range is fromabout 100 W to about 1,000 W, and an example bias voltage is from about−20V to about −1,000V. Where, for example SF₆, O₂, N₂, and HBr areprecursor gases, example flow rates include from about 1 sccm to about100 sccm for SF₆; from about 10 sccm to about 500 sccm for O₂; from 0sccm to about 500 sccm for HBr; and from about 1 sccm to about 500 sccmfor N₂. A specific reduction-to-practice example in the LAM Kiyo plasmaetching chamber included 5 mTorr, 7° C., −500V voltage bias, 400 Wsource power, 350 sccm SF₆, 45 sccm O₂, 60 sccm N₂, and 20 sccm HBr. Theparticular plasma etcher used might be capable of operation such thateither the bias voltage or the bias power can be the set point while theother is allowed to float. In one embodiment, bias voltage is set andbias power is allowed to float. In another embodiment, bias power is setand bias voltage is allowed to float.

It was determined that etching with SF₆ and O₂ without anynitrogen-containing compound may result in significant trench sidewallerosion, irregular trench sidewalls, and/or v-shaped trench bases.However, it was discovered that by adding a nitrogen-containing compoundto the plasma etching chemistry, smoother and/or straighter trenchsidewall resulted and with flatter trench bases, although the inventiondoes not necessarily require achieving any of such results unlessliterally so claimed. Further, and without necessarily being limited byany theory of invention, presence of nitrogen in the plasma may becreating an NF_(x) species that may or may not be facilitatingstraighter sidewalls and flatter bases.

Regardless, one embodiment of the invention includes plasma etchingtrenches into silicon of a semiconductor substrate using a mask havingtrenches formed there-through, wherein the plasma etching comprises anetching plasma comprising a sulfur-containing component, anoxygen-containing component, and NF_(x). In one embodiment, thesulfur-containing component is formed from a precursor gas comprisingSF₆. In one embodiment, the oxygen of the oxygen-containing componentmay be formed from a precursor gas comprising O₂, and the nitrogen ofthe NF_(x) may be formed from a precursor gas compound which is void ofoxygen. Further in one embodiment, the oxygen of the oxygen-containingcomponent and the nitrogen of the NF_(x) may be formed from a precursorgas comprising NO_(x). Further, example precursor gases include any ofthose described above, including any combinations thereof.

Example etch depths for trenches 32 within silicon 12 are from about7,500 Angstroms to about 20,000 Angstroms, with 9,000 Angstroms beingbut one specific example.

Referring to FIGS. 8, 9, and 10, masking layers 40 have been formed oversubstrate 10 and accordingly over first trenches 32 within silicon ofthe substrate. In one embodiment, masking layers 40 comprise multi-layerresist, with three such example layers being sequentially shown ascomprising a first layer 42, a layer 44 thereover, and another layer 45.In one example, layer 42 is in the form of a liquid resin which depositsto completely fill first trenches 32 and be received over hardmask layer26 of first mask 35, and thereafter is solidified. An example layer 44is any silicon-containing hardmask, with an example layer 45 thereovercomprising a photoimageable material such as photoresist.

Referring to FIGS. 11, 12, and 13, photoimageable layer 45 has beenpatterned to form second trenches 50 which run in a second majordirection over substrate 10 which is orthogonal to the first majordirection. The example second major direction in FIG. 13 would beperpendicularly into and out of the plane of the page upon which FIG. 13lies, and in the direction which arrows 13 point in FIG. 11. Further,the first major direction as described above would be in the directionwhich arrows 12 point in FIG. 11. Of course, second trenches 50 mightnot be entirely straight in such second major direction and might, byway of example only, serpentine relative to each other but nevertheless,in one embodiment, run in a second major direction over the substrate asjust described.

Referring to FIGS. 14, 15, and 16, patterned photoimageable material 45(not shown) has been used as a mask to etch silicon-containing hardmasklayer 44, resin 42, and hardmask layer 26 of first mask 35 to extendsecond trenches 50 through hardmask layer 26 to silicon nitride layer24, with photoimageable material 45 being removed during such etchingand/or subsequently.

Referring to FIGS. 17, 18, and 19, etching has been conducted to extendtrenches 50 through silicon nitride layer 24 and pad oxide layer 22 tosilicon material 12. Accordingly, and in but one embodiment, secondtrenches 50 extend through hardmask layer 26 of first mask 35 and asecond mask 55 is formed over the first trenches and comprises hardmasklayer 26 of the first mask.

Referring to FIG. 20, second trenches 50 have been extended into silicon12 by plasma etching thereof using second mask 55. Some of material 42(not shown or viewable in FIG. 20) may remain from the processingdepicted by FIGS. 14, 15, and 16 (not shown), or another materialprovided, at the bases of first trenches 32 (not shown or viewable inFIG. 20) to preclude portions of such first trenches to be etched deeperwhile etching second trenches 50. In one embodiment, the plasma etchingof the second trenches into the silicon comprises forming an etchingplasma using precursor gases comprising SF₆, an oxygen-containingcompound, and a nitrogen-containing compound. Any of the above-describedprocessing might be utilized. Further, the plasma etching to form thesecond trenches within the silicon might be the same as or differentfrom the plasma etching to form the first trenches within the siliconmaterial. Further and regardless, the plasma etching to form the secondtrenches might comprise an etching plasma comprising a sulfur-containingcomponent, an oxygen-containing component, and NF_(x), for example asalso described above. Regardless and by way of example only, exampledepths of trenches 50 within silicon material 12 are from about 2,500Angstroms to about 3,500 Angstroms, with about 3,000 Angstroms being aspecific example.

Some or all of such materials 22, 24, 26, 42, and 44 may or may not beultimately removed from the substrate. FIGS. 21, 22, and 23, by way ofexample only, depict all of such materials having been removed and,regardless, the plasma etching of the second trenches resulting in theformation of spaced silicon-comprising mesas 65.

Embodiments of the invention include methods of forming trench isolationwithin silicon of a semiconductor substrate, and may or may not compriseformation of spaced silicon-comprising mesas. For example and by way ofexample only, the above-described processing after FIGS. 5-7, orotherwise, might include depositing insulative trench isolation materialto within such trenches without necessarily forming the above examplesecond trenches. Further and regardless of forming mesas, insulativetrench isolation material might be deposited to within first and secondtrenches formed within silicon.

Regardless, embodiments of the invention also encompass methods offorming a plurality of diodes in conjunction with forming spacedsilicon-comprising mesas. For example and by way of example only, FIGS.24, 25, and 26 depict subsequent processing whereby insulative material66 has been deposited to be received about spaced silicon-comprisingmesas 65 and a conductive silicide layer 68 has been formed over mesas65. Example insulative materials 66 include one or a combination ofsilicon nitride and silicon dioxide, and a specific example conductivesilicide material 68 includes cobalt silicide. Alternate and/oradditional materials might of course be used. The FIGS. 24-26construction might be fabricated, by way of example only, by depositionof material 66 to overfill the trenches, planarization thereof, andpatterning to expose the silicon-comprising mesas, followed by thesubsequent salicidation of the exposed silicon material of the mesas.

Regardless, FIGS. 24-26 depict formation of individual example diodes 75on individual of the spaced silicon-comprising mesas 65. In oneembodiment, the individual diodes comprise a p-type silicon-comprisingregion (i.e., region 20), and an n-type silicon-comprising region (i.e.,regions 16, 18). In one embodiment, individual diodes comprise asilicon-comprising region (i.e., region 20) and a metal region (i.e.,region 68). By way of example only, the diodes might be used inProgrammable Conductive Random Access Memory (PCRAM) applications.

In compliance with the statute, the subject matter disclosed herein hasbeen described in language more or less specific as to structural andmethodical features. It is to be understood, however, that the claimsare not limited to the specific features shown and described, since themeans herein disclosed comprise example embodiments. The claims are thusto be afforded full scope as literally worded, and to be appropriatelyinterpreted in accordance with the doctrine of equivalents.

1. A method of etching trenches into silicon of a semiconductorsubstrate, comprising: forming a mask over silicon of a semiconductorsubstrate, the mask comprising trenches formed there-through; and plasmaetching trenches into the silicon of the semiconductor substrate usingthe mask, the plasma etching comprising forming an etching plasma usingprecursor gases comprising SF₆, an oxygen-containing compound, and anitrogen-containing compound.
 2. The method of claim 1 wherein theoxygen-containing compound and the nitrogen-containing compound comprisedifferent compounds.
 3. The method of claim 1 wherein theoxygen-containing compound and the nitrogen-containing compound comprisethe same compound.
 4. The method of claim 3 wherein the same compoundcomprises NO_(x).
 5. The method of claim 1 wherein the precursor gasescomprise HBr.
 6. The method of claim 1 wherein the mask comprises anoutermost hardmask layer during at least a latter portion of the plasmaetching into the silicon, said outermost hardmask layer being void ofcarbon.
 7. The method of claim 1 wherein the nitrogen-comprisingcompound comprises N₂.
 8. The method of claim 7 wherein the precursorgases comprise HBr.
 9. The method of claim 1 wherein the precursor gasescomprise two oxygen-containing compounds, one of the oxygen compoundsbeing void of nitrogen, another of the oxygen-containing compoundscomprising the nitrogen-containing compound.
 10. The method of claim 9wherein the one comprises O₂ and the another comprise NO_(x).
 11. Amethod of etching trenches into silicon of a semiconductor substrate,comprising: forming a mask over silicon of a semiconductor substrate,the mask comprising trenches formed there-through; and plasma etchingtrenches into the silicon of the semiconductor substrate using the mask,the plasma etching comprising an etching plasma comprising asulfur-containing component, an oxygen-containing component, and NF_(x).12. The method of claim 11 the sulfur of the sulfur-containing componentis formed from a precursor gas comprising SF₆.
 13. The method of claim11 wherein the oxygen of the oxygen-containing component is formed froma precursor gas comprising O₂, and the nitrogen of the NF_(x) is formedfrom a precursor gas compound which is void of oxygen.
 14. The method ofclaim 11 wherein the oxygen of the oxygen-containing component and thenitrogen of the NF_(x) are formed from a precursor gas comprisingNO_(x).
 15. A method of forming trench isolation in silicon of asemiconductor substrate, comprising: forming a mask over silicon of asemiconductor substrate, the mask comprising trenches formedthere-through; plasma etching trenches into the silicon of thesemiconductor substrate using the mask, the plasma etching comprisingforming an etching plasma using precursor gases comprising SF₆, O₂, andN₂; and depositing insulative trench isolation material to within thetrenches.
 16. The method of claim 15 wherein the precursor gasescomprise HBr.
 17. The method of claim 15 wherein the precursor gasescomprises more N₂ than each of SF₆ and O₂.
 18. The method of claim 15wherein the forming of the etching plasma is from using precursor gasesconsisting essentially of SF₆, O₂, and N₂.
 19. A method of formingtrench isolation in silicon of a semiconductor substrate, comprising:forming a first mask over silicon of a semiconductor substrate, thefirst mask comprising first trenches formed there-through running in afirst major direction over the substrate, the first mask comprising ahardmask layer; plasma etching first trenches into the silicon of thesemiconductor substrate using the first mask, the plasma etching of thefirst trenches into the silicon comprising forming an etching plasmausing precursor gases comprising SF₆, an oxygen-containing compound, anda nitrogen-containing compound; forming a second mask over the firsttrenches, the second mask comprising second trenches formedthere-through running in a second major direction over the substratewhich is orthogonal to the first major direction, the second maskcomprising the hardmask layer of the first mask; plasma etching secondtrenches into the silicon of the semiconductor substrate using thesecond mask, the plasma etching of the second trenches into the siliconcomprising forming an etching plasma using precursor gases comprisingSF₆, an oxygen-containing compound, and a nitrogen-containing compound;and after plasma etching the second trenches, depositing insulativetrench isolation material to within the first and second trenches in thesilicon.
 20. The method of claim 19 wherein the second mask is formedfrom multilayer resist received over the hardmask layer of the firstmask.
 21. The method of claim 19 wherein the hardmask layer of the firstmask is insulative.
 22. The method of claim 19 wherein the hardmasklayer of the first mask is conductive.
 23. The method of claim 22wherein the conductive hardmask layer of the first mask comprises atleast one of a refractory metal nitride, a refractory metal silicide, ora metal in elemental-form.
 24. A method of forming a plurality ofdiodes, comprising: forming a first mask over silicon of a semiconductorsubstrate, the first mask comprising first trenches formed there-throughrunning in a first major direction over the substrate, the first maskcomprising a hardmask layer; plasma etching first trenches into thesilicon of the semiconductor substrate using the first mask, the plasmaetching of the first trenches into the silicon comprising forming anetching plasma using precursor gases comprising SF₆, anoxygen-containing compound, and a nitrogen-containing compound; forminga second mask over the first trenches, the second mask comprising secondtrenches formed there-through running in a second major direction overthe substrate which is orthogonal to the first major direction, thesecond mask comprising the hardmask layer of the first mask, the secondtrenches extending through the hardmask layer of the first mask; plasmaetching second trenches into the silicon of the semiconductor substrateusing the second mask, the plasma etching of the second trenches intothe silicon comprising forming an etching plasma using precursor gasescomprising SF₆, an oxygen-containing compound, and a nitrogen-containingcompound, the plasma etching of the second trenches into the siliconforming spaced silicon-comprising mesas; and providing individual diodeson individual of the mesas and depositing insulative material to bereceived about the spaced silicon-comprising mesas.
 25. The method ofclaim 24 wherein the individual diodes comprise a p-typesilicon-comprising region and an n-type silicon-comprising region.